Perspectives on SnSe-based thin film solar cells: a comprehensive review

Currently, selenium (Se)-based compound semiconductors (CISe, CIGSe and CZTSe) are considered as the active materials in the photovoltaic world. However, these materials exhibit couple of issues related to stoichiometry maintenance and scarcity of their constituent elements (In, Ga), which limit their massive production for future energy demands. These issues could be rectified by introducing a non-toxic, inexpensive and earth-abundant binary material. One such material is a tin monoselenide (SnSe), which exhibits a high chemical stability along with attractive physical properties namely, suitable band gap (1.3 eV), high absorption coefficient (10⁵ cm^?1) and p-type conductivity. These properties indicate SnSe as a competitive substitute in place of conventional absorbers in thin film solar cells. Despite of its remarkable properties, only a few reports were published on the fabrication of SnSe-based solar cells with poor efficiency (≤1 %). This indicates a need to review on the physical properties of SnSe and its device structures in a deeper sense. In this context, the present review describes the different methods of preparation of SnSe films and their physical properties along with the details of photovoltaic device fabrication. We highlighted the different factors that are limiting the efficiency of SnSe solar cells, and a few suggestions were included to overcome these problems for further improvement of these cells. This review will enrich and stimulate the readers to further investigate the growth of SnSe thin films and their devices, for the development of >20 % efficient SnSe solar cells.     

Electrical characteristics and detailed interfacial structures of Ag/Ni metallization on polycrystalline thermoelectric SnSe

SnSe is a promising thermoelectric material with a high figure of merit in single crystal form, which has stimulated continuous research on polycrystalline SnSe. In this study, we investigated a metallization techniques for polycrystalline SnSe to achieve highly efficient and practical SnSe thermoelectric modules. The Ag/Ni metallization layers were formed on pristine polycrystalline SnSe using various deposition technique: sputter coating Ni, powder Ni and foil Ni by spark plasma sintering. Structural analysis demonstrated that the microstructure and contact resistance could be different according to the metallization process, despite using the same metals. The Ag/Ni metallization layer using foil Ni acted as an effective diffusion barrier and minimized electrical contact resistance(2.3 × 10~(-4) Ω cm~2). A power loss in the thermoelectric module of only 5% was demonstrated using finite element simulation.     

The fabrication of SnSe/Ag nanoparticles on TiO2 nanotubes

SnSe and silver (Ag) nanoparticles were sequentially deposited on TiO₂ nanotube (NT) by pulsed electrochemical deposition and polyol chemistry process, respectively. The morphological observation under scanning electron microscope (SEM) showed that the average size of SnSe was about 30 nm and the Ag was about 5 nm. Transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED) examination indicated that Ag nanoparticles exhibited a well-defined crystallinity. However, SnSe nanoparticles were amorphous and they turned to crystalline after being annealed at 300 °C in the atmosphere. The photocatalytic behavior of SnSe/Ag-TiO₂ NT was evaluated by UV–vis diffuse reflectance spectra (DRS). The results showed that the deposition of SnSe and Ag nanoparticles increased light absorption intensity in the wavelength range of visible light, which implied that the SnSe/Ag-TiO₂ NT is a promising ternary hybrid material in photocatalysis.     

A facile way to optimize thermoelectric properties of SnSe thin films via sonication-assisted liquid-phase exfoliation

In our work, SnSe nanosheets and nanostructured thin films were successfully synthesized via sonication-assisted exfoliation and coating process. The SnSe nanosheets respond to a uniform lateral size, with two to three single layers by 2.82 nm and 280 nm² of average thickness and average area, respectively. The results were confirmed by Scanning Electron Microscope, Transmission Electron Microscope, and Atomic Force Microscope. X-ray diffraction and Raman spectra indicate that the SnSe nanosheets have high crystalline quality along a-axis. The SnSe nanostructured thin films were prepared in various thicknesses from 350 to 650 nm. The highest power factor value is achieved at 450 nm in 375–600 K temperature range. A simple method of fabrication and controllable thermoelectric properties of SnSe nanostructured thin films as well as other two-dimensional (2D) materials are introduced.

     

In situ high resolution transmission electron microscopy investigation of deformation mechanism in sub-10-nm Au crystals

Abstract

In situ high resolution transmission electron microscopy investigations were performed on sub-10-nm Au crystals. The effects of tensile loading direction and crystal size on the deformation mechanism of Au crystals were analysed. For the Au crystals with a width below 2 nm, the surface atom diffusion with a phenomenon of layer by layer peeling is the main deformation mechanism and the tensile loading direction plays negligible effect. For the Au crystals with a width over 7 nm, the dislocations generated form surface and gliding into crystal dominate the plastic deformation and the tensile loading direction plays important role. Lomer dislocations are produced and destructed by dislocation reaction during tensile strain process in <001> oriented Au crystal. The Schmid law is the key intrinsic issue controlling the deformation mechanism for the nanowires with a size larger than 7 nm.     

Synthesis and properties of model SiC-Si3N4 interfaces

Microscopic and macroscopic SiC-Si₃N₄ interfacial structures were synthesized and their properties examined. Microscopic interfaces were produced by hot isostatic pressing vapour-liquid-solid SiC whisker-polycrystalline Si₃N₄ matrix composites without densification aids. Macroscopic interfaces were formed by the chemical vapour deposited Si₃N₄ coating of large SiC single crystals. The characteristics of these model interfaces were investigated using transmission electron microscopy and indentation fracture. Results showed the microscopic interfaces to contain a small amount of second phase, while the macroscopic interfaces were pristine in nature with no second phase present. Pristine SiC-Si₃N₄ interfaces were strongly bonded at room temperature, but interfacial strength decreased at elevated temperatures.     

Electrical resistivity anisotropy in layered p-SnSe single crystals

Single crystals of p-type SnSe were grown by both direct vapor transport (DVT) and chemical vapor transport (CVT) techniques. The d.c. electrical resistivity anisotropy has been investigated for the first time in these layered crystals. The DVT grown crystals exhibited a large anisotropy ratio and also a higher activation energy compared to that of CVT grown crystals. The electron microscopic examination revealed the presence of a large concentration of stacking faults in the DVT grown crystals. The resistivity anisotropy is accordingly discussed in terms of stacking disorder.     

Advanced Hybrid GaN/ZnO Nanoarchitectured Microtubes for Fluorescent Micromotors Driven by UV Light

The development of functional microstructures with designed hierarchical and complex morphologies and large free active surfaces offers new potential for improvement of the pristine microstructures properties by the synergistic combination of microscopic as well as nanoscopic effects. In this contribution, dedicated methods of transmission electron microscopy (TEM) including tomography are used to characterize the complex hierarchically structured hybrid GaN/ZnO:Au microtubes containing a dense nanowire network on their interior. The presence of an epitaxially stabilized and chemically extremely stable ultrathin layer of ZnO on the inner wall of the produced GaN microtubes is evidenced. Gold nanoparticles initially trigger the catalytic growth of solid solution phase (Ga_1–xZn_x)(N_1–xO_x) nanowires into the interior space of the microtube, which are found to be terminated by AuGa‐alloy nanodots coated in a shell of amorphous GaO_x species after the hydride vapor phase epitaxy process. The structural characterization suggests that this hierarchical design of GaN/ZnO microtubes could offer the potential to exhibit improved photocatalytic properties, which are initially demonstrated under UV light irradiation. As a proof of concept, the produced microtubes are used as photocatalytic micromotors in the presence of hydrogen peroxide solution with luminescent properties, which are appealing for future environmental applications and active matter fundamental studies.     

Investigation of inter-diffusion in bilayer GeTe/SnSe phase change memory films

A metal-chalcogenide layer, SnSe, is inserted between the memory layer GeTe and the top electrode to form a phase change memory cell. The GeTe layer exhibits ovonic threshold switching at a threshold field of ~ 110 V/μm. For subsequent implementation into applications and reliability, material inter-diffusion and sublimation are examined in bilayer phase change films of GeTe/SnSe. Transmission electron microscopy and parallel electron energy loss spectroscopy analyses reveal Sn migration to the GeTe layer, which is responsible for lowering the rhombohedral to cubic structural transformation temperature in GeTe. Incongruent sublimation of SnSe and GeTe is observed at temperatures higher than 500 °C. Severe volatilization of Se results in the separation of a metallic Sn phase. The use of Al₂O₃ as a capping layer has been found to mitigate these effects.     

Ag掺杂SnSe化合物的制备及热电性能

SnSe是一种潜在的极具应用前景的热电材料。采用机械合金化结合放电等离子烧结的方法制备了Ag掺杂的Sn_1-xAg_xSe (0.005≤x≤0.03)多晶块体热电材料, 并借助XRD、SEM、电热输运测试系统研究了其物相组成、微结构与电热输运性能。XRD分析结果表明, 少量Ag(0.005≤x≤0.01)掺杂仍然能够成功制备出单相斜方结构SnSe化合物, 但随着Ag掺杂量的增加, 基体中出现SnAgSe₂第二相, 且第二相含量逐渐增加。掺杂Ag大幅度提高了载流子浓度, 从而使材料的综合电输运性能(功率因子)显著提高, 当Ag掺杂量x=0.02时, 功率因子提高至4.95×10^-4 W/(m·K²), 较未掺杂SnSe样品提高了36%。尽管掺杂样品的热导率均有小幅升高, 无量纲热电优值(ZT)仍获得一定改善。当Ag掺杂量x=0.02时, Sn_0.98Ag_0.02Se成分样品具有较高的热电优值, 并在823 K附近达到最高值0.82。     

磁控溅射沉积制备SnSe薄膜及其热电性能研究

因为晶体结构以及热电性能各向异性,硒化锡(SnSe)沿b轴方向表现出优异的热电性能,受到业内的广泛关注.但关于SnSe薄膜研究的报道较少.本研究利用磁控溅射技术,将SnSe沉积到Si/SiO2基底得到SnSe薄膜,分析了沉积温度对SnSe薄膜结构和热电性能的影响.结果显示:沉积温度升高,晶粒尺寸相应增加,薄膜的结晶质量...     

Anisotropic photoresponse investigation of chemical vapor transport (CVT) grown quaternary Cu2ZnSnS4 single crystals

The single crystals of quaternary transition metal chalcogenide Cu₂ZnSnS₄ (CZTS) are grown by a closed system chemical vapor transport technique. The high purity individual elemental precursors are employed in the growth of the crystals. These crystals are found to be single-phase by X-ray diffraction and Raman analysis. The near stoichiometry of the grown crystals is confirmed by spectroscopy analysis of the photoelectron generated by X-rays and analysis of the energy of the dispersive X-rays generated by electrons. The surface study by scanning electron microscopy showed the growth to happen by sheet spread mean and the electron diffraction showed fringe width match with (112) plane spacing. The study of the CZTS/Ag-paste/Cu-wire system for incident white light and three wavelengths of laser lights in two configuration modes of top-contact (II to the plane) and bottom-top-contact (⊥ to the plane) showed anisotropic behavior. The incident white light illumination intensity of 120 mW/cm² showed utmost photoresponse. The top-contact mode configuration showed maximum responsivity and detectivity of 0.72 mA/W and 0.33 × 10⁹ Jones, respectively, while bottom-top-contact showed 0.18 mA/W and 0.13 × 10⁹ Jones, respectively. The anisotropic photoresponse by the CZTS crystals insinuates the potential for future applications.

     

Microstructure and thermal change of texture of calcite crystals in ostrich eggshell Struthio camelus

Eggshell from ostrich Struthio camelus, pristine and thermally treated in the range from room temperature to 550 °C, was investigated with low vacuum scanning electron microscopy (LVSEM), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray powder diffractometry (XRD). Different zones of the eggshell were analysed, including the protein-related, non-crystalline, inner organic membrane. After the high-temperature treatment (>500 °C), only crystallised calcite phase was found showing two main textures depending on the shell zone and the treatment temperature. In the crystal layer of the untreated samples, nanosized calcite crystals are organized with their c crystallographic axes highly aligned normal to eggshell surface (a very sharp gaussian angular distribution, σ=0.14, was obtained by using the Rietveld method to model the preferred orientation function in the X-ray powder diffraction pattern). Elemental analysis revealed more Mg²⁺ in the crystal layer than in cone layer of the eggshell. A high nitrogen content in the organic membrane is associated to a proteinaceous phase. The cone and palisade layers are composed of needle-shaped calcite crystals, which are more crystallized than in the crystal layer and in average with their c crystallographic axes oriented in all directions except for the one perpendicular to the eggshell surface. Due to the complex structure and the amorphous/crystal phase interactions, the heating at about 500 °C texturizes the crystals orienting them mainly along the c-axes normal to the inner eggshell surface.     

Growth of calcium carbonate on non-covalently modified carbon nanotubes

The crystallization of calcium carbonate was investigated on pristine and non-covalently modified carbon nanotubes (CNTs) using the vapor diffusion technique in a calcium chloride solution. Non-covalent modification was accomplished by treating the carbon nanostructures with the amphiphilic copolymer poly(isoprene-b-acrylic acid). Calcium carbonate crystals grown on the surface and in the interstitial channels of CNT buckypapers were observed in both cases. Scanning electron microscopy analysis of the untreated CNTs showed the characteristic rhombohedral morphology of calcite crystals, while in the case of modified material spherical and ellipsoidal crystals, consisted of nanocrystallites, were observed. X-ray diffraction analysis showed the presence of calcite crystals in both cases.     

Complex oxide structures formed by oxidation of Ag(100) and Ag(111) by hyperthermal atomic oxygen

Abstract

Silver (100) and (111) single crystals were exposed to a unique hyperthermal atomic oxygen source, which produces a high flux of 5.1eV atomic oxygen, for seven hours at 220°C. The resultant oxide and oxide–metal interfaces were characterized by optical, scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HREM). The oxide scale was more than 10 µm thick and very weakly attached to the Ag substrate. The silver oxides were complex and surprising, differ in their thickness and the oxide phases due to the orientation of the Ag single crystals. The cross-section TEM studies revealed complex microstructures with many defects, such as micro-twins, porosity and irregular shaped grains.     

Present status and future prospects of spherical aberration corrected TEM/STEM for study of nanomaterials∗

Abstract

The present status of Cs-corrected TEM/STEM is described from the viewpoint of the observation of nanomaterials. Characteristic features in TEM and STEM are explained using the experimental data obtained by our group and other research groups. Cs correction up to the 3rd-order aberration of an objective lens has already been established and research interest is focused on correcting the 5th-order spherical aberration and the chromatic aberration in combination with the development of a monochromator below an electron gun for smaller point-to-point resolution in optics. Another fundamental area of interest is the limitation of TEM and STEM resolution from the viewpoint of the scattering of electrons in crystals. The minimum size of the exit-wave function below samples undergoing TEM imaging is determined from the calculation of scattering around related atomic columns in the crystals. STEM does not have this limitation because the resolution is, in principle, determined by the probe size. One of the future prospects of Cs-corrected TEM/STEM is the possibility of extending the space around the sample holder by correcting the chromatic and spherical aberrations. This wider space will contribute to the ease of performing in situ experiments and various combinations of TEM and other analysis methods. High-resolution, in situ dynamic and 3D observations/analysis are the most important keywords in the next decade of high-resolution electron microscopy.     

Thin Film Tin Selenide (SnSe) Thermoelectric Generators Exhibiting Ultralow Thermal Conductivity

Tin selenide (SnSe) has attracted much attention in the field of thermoelectrics since the discovery of the record figure of merit (ZT) of 2.6 ± 0.3 along the b‐axis of the material. The record ZT is attributed to an ultralow thermal conductivity that arises from anharmonicity in bonding. While it is known that nanostructuring offers the prospect of enhanced thermoelectric performance, there have been minimal studies in the literature to date of the thermoelectric performance of thin films of SnSe. In this work, preferentially orientated porous networks of thin film SnSe nanosheets are fabricated using a simple thermal evaporation method, which exhibits an unprecedentedly low thermal conductivity of 0.08 W m^?1 K^?1 between 375 and 450 K. In addition, the first known example of a working SnSe thermoelectric generator is presented and characterized.     

Solid phase growth of tin oxide nanostructures

For the first time, single-crystalline SnO₂ nanostructures comprising of nanobelts, nanowires and nanosheets have been synthesised by solid phase crystal growth from tin oxide single crystals. The product was characterised by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy, selected area electron diffraction, and Raman spectroscopy. The procedure consisted of two stages. In the first stage, a mixture of SnO₂ polyhedral single crystals attached with graphite particles were produced by heating a mixture of SnCl₂ and graphite. Then, the SnO₂ single crystals were grown into nanobelts, nanowires and nanosheets by further heating. The role of graphite in the process is also discussed to be the surface reduction of SnO₂ into oxides with lower oxygen content which provide a driving force for surface diffusion and subsequent crystal growth of tin oxide into the one and two dimensional nanostructures. The results provide insights for both fundamental research as well as technological production of SnO₂ nanostructures.     

The effects of S-doping concentration on the photocatalytic performance of SnSe/S-GO nanocomposites

The effects of S-doped graphene oxide (S-GO) on the photocatalytic performance of SnSe nanostructures have been investigated. Different concentrations of S-doping as 2S-GO, 4S-GO, and 6S-GO (2, 4, and 6% in weight) have been synthesized. Characterization results indicated sulfur not only has successfully placed in the GO structure and a part of the GO sheet has been changed into reduced GO (rGO) by sulfur doping but also the surface morphology of the GO sheets has been changed from a smooth surface to fractured crack surfaces. The results showed that the increase of sulfur content caused the morphology of the SnSe nanostructures was changed from nanoparticles (NPs) into nanorods (NRs). The photocatalytic activity of the samples to degrade dyes under the visible-light irradiation conditions was carried out and it was observed an enhancement photocatalytic performance for the SnSe/2S-rGO nanocomposites in comparison to the other samples. More than 95% of dyes were degraded by the SnSe/2S-rGO nanocomposites for only 60 min. Brunauer–Emmett–Teller (BET) and electrical measurement results indicated the textural properties and conductivity of GO sheets were improved by sulfur doping. In addition, the photogenerated electron lifetime (τ_r) of the SnSe/rGO and SnSe/S-rGO nanocomposites has been measured by the Bode phase plot and it was observed a lifetime of τ_r = 71.1 and 31.7 μs for the SnSe/S-rGO and SnSe/rGO nanocomposites, respectively.     

Preparation of superhydrophobic surfaces on cotton textiles

Abstract

Superhydrophobic surfaces were fabricated by the complex coating of silica nanoparticles with functional groups onto cotton textiles to generate a dual-size surface roughness, followed by hydrophobization with stearic acid, 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane or their combination. The wettability and morphology of the as-fabricated surfaces were investigated by contact angle measurement and scanning electron microscopy. Characterizations by transmission electron microscopy, Fourier transformation infrared spectroscopy, and thermal gravimetric analysis were also conducted.